Process for the preparation of triphendioxazine dyestuffs amidated on both sides, and novel triphendioxazine dyestuffs

ABSTRACT

According to the invention, a process for the preparation of triphendioxazines systemetrically or asymmetrically amidated on both sides comprises reducing a triphendioxazine chromophore, which is optionally already amidated on one side, to give the leuco form end amidating and re-oxidizing the leuco form. Products amidated on both sides are obtained in this manner with a high yield and product quality. Novel triphendioxazine dyestuffs are furthermore prepared in this manner.

This application is a divisional of application Ser. No. 08/744,422,filed Nov. 8, 1996, now U.S. Pat. No. 5,696,258.

DESCRIPTION

Process for the preparation of triphendioxazine dyestuffs amidated onboth sides, and novel triphendioxazine dyestuffs

The present invention lies in the field of triphendioxazine textiledyestuffs.

Triphendioxazines are tinctorially strong dyestuffs which are suitableboth as direct dyestuffs and as reactive dyestuffs. However, thecorresponding dyestuff hydrolysates are often difficult to wash out, andthe levelness of the dyeings is unsatisfactory.

Dioxazines amidated on both sides have already been described frequentlyin the technical literature (for example U.S. Pat. No. 4,933,446, U.S.Pat. No. 5,486,607 and U.S. Pat. No. 3,883,523). However, the compoundsamidated on one side are frequently chiefly formed in the proceduresdescribed, often in contrast to the statements made, or the productsdescribed as being amidated on both sides are formed only inunsatisfactory yields. Thus, the compounds amidated on one side areroyal blue, while the compounds amidated on both sides are violet orvery reddish-tinged blue. It is furthermore known that an increasinglyredder product is formed with excess amidating agents (U.S. Pat. No.3,883,523), from which partial double amidation can be concluded,although this is achieved selectively in the rarest of cases.

Moreover, customary methods to date for preparation of suchtriphendioxazine dyestuffs, for example U.S. Pat. No. 5,486,607, U.S.Pat. No. 5,272,267, U.S. Pat. No. 5,438,137 and U.S. Pat. No. 4,933,446,give yields and product qualities which are in need of improvement.

"Amidated triphendioxazine compounds" in the present Application meansthose compounds in which the exocyclic nitrogen atoms of thetriphendioxazine chromophore are bonded with an acyl radical, anaminocarbonyl radical, a sulfonyl radical or a nitrogen-containingheteroaromatic radical.

The object of the present invention was to provide a process for thepreparation of triphendioxazine dyestuffs which overcomes thedisadvantages of the prior art in respect of yield and product quality.

Another object of the present invention was to provide an advantageousmethod for the preparation of triphendioxazines amidated on both sides.

Another object of the invention was to provide novel triphendioxazinedyestuffs, in particular those having a violet or reddish-tinged blueshade.

It has been found that the objects mentioned are achieved, surprisingly,by reduction of the triphendioxazine chromophore, which is optionallyalready amidated on one side, to the leuco form, amidation at the stageof the leuco form and reoxidation.

The invention relates to a process for the preparation oftriphendioxazine compounds of the formula (1) ##STR1## in which R₁ ishydrogen or C₁ -C₄ -alkyl, which can be substituted by 1 or 2substituents from the series consisting of hydroxyl, C₁ -C₄ -alkoxy,sulfato or sulfo;

R₂ has one of the meanings of R₁ ;

E is sulfo, carboxyl, C₁ -C₄ -alkylsulfonyl or a radical SO₂ Y, in whichY is vinyl or CH₂ CH₂ V, in which V is hydroxyl, or is a leaving groupfrom the series consisting of sulfato, phosphate, thiosulfato orhalogen, such as chlorine;

or is --SO₂ NR₃ R₄ or --CONR₃ R₄, in which

R₃ is hydrogen, phenyl, or C₁ -C₄ -alkyl, which can be substituted byhydroxyl, carboxyl, sulfo, sulfato or a radical SO₂ Y,

R₄ has one of the meanings of R₃, or, together with R₃ and N, forms a 5-or 6-membered heterocyclic radical, which can be interrupted by 1 to 3further heteroatoms from the series consisting of N, O and S;

X₁ is halogen, such as chlorine or bromine, in particular chlorine,hydrogen, C₁ -C₆ -alkyl, such as methyl, ethyl or isopropyl, phenyl,phenoxy or C₁ -C₄ -alkoxy;

X₂ has one of the meanings of X₁ ;

V₁ is hydrogen, sulfo, methoxy, methyl or halogen, such as chlorine;

V₂ has one of the meanings of V₁ ; and

Z₁ and Z₂ are identical or different and are an acyl radical, anunsubstituted, alkylated or arylated aminocarbonyl radical, a sulfonylradical or a nitrogen-containing heteroaromatic radical,

which comprises reducing a compound of the formula (2) ##STR2## in whichT is hydrogen, Z₁ or Z₂, to give a compound of the formula (3) ##STR3##reacting this with a reactive derivative on which the radical Z₁ and/orZ₂ is based, to give a compound of the formula (4) ##STR4## andsubsequently oxidizing this to give the triphendioxazine compound of theformula (1).

It is known from Bull. Chem. Soc. Jpn. 56 (1983), 1482 that9,13-dichorotriphendioxazines can be dehalogenated in the 9- and13-positions with tin in polyphosphoric acid. However, instead of thedehatogenation expected from knowledge of the prior art, surprisingly, areduction to the leuco base takes place if the reaction according to theinvention is carried out in an aqueous medium in the presence ofreducing agents. The reduction is completely reversible, and thetriphendioxazine color base is obtained again by oxidation.

E is preferably sulfo, --SO₂ --CH₂ CH₂ --OSO₃ M, --SO₂ --CH═CH₂, --SO₂--CH₂ CH₂ Cl or --SO₂ --CH₂ CH₂ OH.

X.sub. and X₂ are referably chlorine.

V₁ is preferably hydrogen.

V₂ is preferably hydrogen or sulfo, in particular hydrogen.

R₁ and R₂ are preferably hydrogen.

R₃ is preferably hydrogen, methyl or phenyl.

The radicals Z₁ and Z₂ are preferably C₁ -C₆ -alkylcarbonyl, C₂ -C₄-alkenylcarbonyl, C₆ -arylcarbonyl, aminocarbonyl, C₁ -C₆-alkylaminocarbonyl, di-(C₁ -C₆)-alkylaminocarbonyl, C₆-arylaminocarbonyl or C₆ -arylsulfonyl, in which the alkyl and arylradicals can be substituted by 1 to 3, preferably 1, identical ordifferent substituents from the series consisting of SO₂ Y, sulfo,carboxyl, hydroxyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkyl, cyano, halogen,acylamino, such as acetylamino, and nitro.

In the case where Z₁ and/or Z₂ are a nitrogen-containing heterocyclicradical, heterocycles from the series consisting of the triazines,pyrimidines and quinoxalines are preferred.

Particularly preferred radicals here are those of the formulae (5a) to(5d) ##STR5## in which p is 0 or 1, preferably 0;

A₁ is chlorine, fluorine, C₁ -C₄ -alkoxy, phenoxy, hydroxyl, amino,cyanamino or pyridinyl which is optionally substituted by carboxyl oraminocarbonyl, or a radical NR₇ R₈, wherein

R₇ is hydrogen, C₁ -C₄ -alkyl, which can be substituted by 1 or 2,preferably 1, identical or different substituents from the seriesconsisting of hydroxyl, sulfo, sulfato and carboxyl, or phenyl, whichcan be substituted by 1 to 3 identical or different substituents fromthe series consisting of methoxy, methyl, halogen, sulfo or carboxyl,

R₈ is hydrogen or C₁ -C₄ -alkyl, which can be substituted by 1 to 2,preferably 1, substituents from the series consisting of hydroxyl,sulfo, sulfato and carboxyl,

or R₇ and R₈, together with the N atom, form a saturated 5- to7-membered heterocyclic radical, which can also contain 1 or 2 others ofthe hetero groups N, O, S and/or SO₂, for example piperidine,morpholine, pyrrolidine, piperazine, thiomorpholine or thiomorpholinedioxide, in particular morpholine;

A₂ has one of the meanings of A₁ and is, in particular, chlorine,fluorine or cyanoamino;

A₁ has one of the meanings of A₁ ;

U is a bridge member from the series consisting of --NH--C₁ -C₆-alkylene-NH--, --NH--C₆ -arylene-NH--, in which arylene can besubstituted by 1 or 2 sulfo, carboxyl, methyl and/or methoxy radicals,##STR6## B₁ is hydrogen, chlorine, fluorine, trichloromethyl,trifluoromethyl or methylsulfonyl;

B₂ is hydrogen, chlorine, methyl, methylsulfonyl or fluorine; and

B₃ is hydrogen, cyano, fluorine or chlorine,

with the proviso that at least one of the radicals B₁ or B₂ is a leavinggroup from the series consisting of chlorine, fluorine andmethylsulfonyl.

The bridge member U is particularly preferably a radical of the formula--NH--CH₂ --CH₂ --NH--, --NH--(CH₂)₃ --NH--, ##STR7##

The abovementioned radical NR₇ R₈ is particularly preferably a structureof the formulae (6a) to (6d) ##STR8## in which U₂ is a chemical bond,--CH₂ --, --O--, --NH--, >N--(CH₂)₂ OH, --S-- or --SO₂ --;

y is 1 or 2;

M is hydrogen or an alkali metal, such as Li, Na or K, and

L is hydroxyl, sulfo, sulfato or carboxyl.

Z₁ and Z₂ furthermore preferably represent a fiber-reactive radical ofthe formula (5e) ##STR9## in which Q is halogen, such as chlorine orfluorine, hydroxyl, cyanoamino or a radical NR₃₀ --W--SO₂ Y;

W is C₂ -C₆ -alkylene, which can be interrupted by a hetero group O, S,NH or SO₂ ; phenylene, which can be substituted by methoxy or sulfo; oraralkylene, such as --CH₂ -phenylene or -phenylene--CH₂ --;

R₃₀ is hydrogen, C₁ -C₄ -alkyl, phenyl, which can be substituted by asulfo group, or the radical --W₁ --SO₂ Y, in which W₁ is C₂ -C₆ -alkyl,and

Y has one of the abovementioned meanings.

Particularly preferably, W is --(CH₂)₂ --, --(CH₂)₃ --, --(CH₂)₂O--(CH₂)₂ --, 1,4-phenylene or 1,3-phenylene and R₃₀ is hydrogen, methylor phenyl.

The radical NR₃₀ --W--SO₂ Y is particularly preferably one of theformulae defined below ##STR10## in which Y¹ is vinyl, β-hydroxyethyl,β-chloroethyl or β-sulfatoethyl.

Particularly preferred radicals Z₁ and Z₂ are ##STR11## in which x is 2or 3;

y is 1 or 2;

U₂ has one of the abovementioned meanings;

L is hydroxyl, sulfo, carboxyl or sulfato;

Y¹ has one of the abovementioned meanings;

Hal is chlorine or fluorine, and

M is hydrogen or an alkali metal.

Examples of the radical NR₃₀ --W--SO₂ Y are

N-phenyl-3-(β-sulfatoethylsulfonyl)-propylamino,

N-methyl-2-(β-sulfatoethylsulfonyl)-ethylamino,

N-phenyl-2-(β-sulfatoethylsulfonyl)-ethylamino,

3-(β-sulfatoethylsulfonyl)-propylamino,

bis-{3-(β-sulfatoethylsulfonyl)-propyl}-amino,

bis-{2-(β-sulfatoethylsulfonyl)-ethyl}-amino,

bis-{3-(β-chloroethylsulfonyl)-propyl}-amino,

bis-{2-(β-chloroethylsulfonyl)-ethyl}-amino,

N-phenyl-3-(vinylsulfonyl)-propylamino,

N-phenyl-2-(vinyisulfonyl)-ethylamino, 3-(vinylsulfonyl)-propylamino,

bis-{3-(vinylsulfonyl)-propyl}-amino,bis-{2-(vinylsulfonyl)-ethyl}-amino,

3-(β-sulfatoethylsulfonyl)-phenylamino,

4-(β-sulfatoethylsulfonyl)-phenylamino,

2-methoxy-5-(β-sulfatoethylsulfonyl)-phenylamino,

2,5-dimethoxy-4-(β-sulfatoethylsulfonyl)-phenylamino and

2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)-phenylamino.

Examples of radicals of the formula Z₁ and/or Z₂ are

phenylsulfonyl, 4-methylphenylsulfonyl, 4-acetylaminosulfonyl,

phenylaminocarbonyl, aminocarbonyl, benzoyl, 2-carboxybenzoyl,

4-carboxybenzoyl, 3-(β-chloroethylsulfonyl)-benzoyl, 3-nitrobenzoyl,

4-nitrobenzoyl, acetyl, propionyl, 2-carboxy-acryloyl,2-carboxy-propionyl,

2,4-dichloro-triazin-6-yl,2-(2'-sulfophenyl)amino-4-chloro-triazin-6-yl,

2-(3'-sulfophenyl)amino-4-chloro-triazin-6-yl,

2-(4'-sulfophenyl)amino-4-chloro-triazin-6-yl,

2-(2',5'-disulfophenyl)amino-4-chloro-triazin-6-yl,

2-cyanoamino-4-chloro-triazin-6-yl, 2-phenoxy-4-chloro-triazin-6-yl,

2-methoxy-4-chloro-triazin-6-yl, 2-amino-4-chloro-triazin-6-yl,

2-(β-sulfoethyl)amino-4-chloro-triazin-6-yl,

2-(N-β-sulfoethyl-N-methyl-)amino-4-chloro-triazin-6-yl,

2-(β-sulfoethyl)amino-4-fluoro-triazin-6-yl,

2-(N-β-sulfoethyl-N-methyl-)amino-4-fluoro-triazin-4-yl,

bis-{2,4-(β-sulfoethyl)amino}-triazin-6-yl,

bis-{2,4-(β-hydroxyethyl)amino}-triazin-6-yl,2,4-dicyanoamino-triazin-6-yl,

2-(β-sulfoethyl)amino-4-cyanoamino-triazin-6-yl,

4-fluoro-2-{N-phenyl-2'-(β-sulfatoethyl)sulfonyl-ethyl-amino}-triazin-6-yl,

4-fluoro-2-{N-phenyl-3'-(β-sulfatoethyl)sulfonyl-propyl-amino}-triazin-6-yl,

4-fluoro-2-{N-methyl-2'-(β-sulfatoethyl)sulfonyl-ethyl-amino}-triazin-6-yl,

4-fluoro-2-{3'-(β-sulfatoethyl)sulfonyl-propyl-amino}-triazin-6-yl,

4-chloro-2-{N-phenyl-2'-(β-sulfatoethyl)sulfonyl-ethyl-amino}-triazin-6-yl,

4-chloro-2-{N-phenyl-3'-(β-sulfatoethyl)sulfonyl-propyl-amino}-triazin-6-yl,

4-chloro-2-{N-methyl-2'-(β-sulfatoethyl)sulfonyl-ethyl-amino}-triazin-6-yl,

4-chloro-2-{3'-(β-sulfatoethyl)sulfonyl-propyl-amino}-triazin-6-yl,

4-cyanoamino-2-{N-phenyl-2'-(β-sulfatoethyl)sulfonyl-ethyl-amino}-triazin-6-yl,

4-cyanoamino-2-{N-phenyl-3'-(β-sulfatoethyl}-sulfonyl-propyl-aminor-triazin

4-chloro-2-{4'-(β-sulfatoethyl)sulfonyl-phenyl-amino}-triazin-6-yl,

4-cyanoamino-2-{4'-(β-sulfatoethyl)sulfonyl-phenyl-amino}-triazin-6-yl

4-chloro-2-{3'-(β-sulfatoethyl)sulfonyl-phenyl-amino}-triazin-6-yl,

4-cyanoamino-2-{3'-(β-sulfatoethyl)sulfonyl-phenyl-amino}-triazin-6-yl

4-chloro-2-{2'-methoxy-5'-(β-sulfatoethyl)sulfonyl-phenyl-amino}-triazin-6-yl

4-cyanoamino-2-{2'-methoxy-5'-(β-sulfatoethyl)sulfonyl-phenyl-amino}-triazin-6-yl,

4-fluoro-2-{4'-(β-sulfatoethyl)sulfonyl-phenyl-amino}-triazin-6-yl,

4-fluoro-2-{4'-(β-sulfatoethyl)sulfonyl-phenyl-amino}-triazin-6-yl,

2,4-difluoro-pyrimidin-6-yl, 2,4-difluoro-5-chloro-pyrimidin-6-yl,

2,4,5-trichloro-pyrimidin-6-yl, 2-fluoro-5-chloro-pyrimidin-6-yl,

5-cyano-2,4-dichloro-pyrimidin-6-yl,2-methylsulfonyl-4-methyl-5-chloro-pyrimidin-6-yl,2-fluoro-4-methyl-5-chloro-pyrimidin-6-yl,5-chloro-4-fluoropyrimidin-6-yl,

4,5-difluoro-2-trifluormethyl-pyrimidin-6-yl,2,5-dichloro-4-fluoro-pyrimidin-6-yl,

2-fluoro-4,5-dichloro-pyrimidin-6-yl, 4-fluoropyrimidin-6-yl,2-fluoropyrimidin-6-yl, and 2-fluoro-5-chloro-pyrimidin-6-yl.

In the process according to the invention for the preparation of thetriphendioxazine compounds of the formula (1) mentioned, which areamidated on both sides, the compound of the formula (2) is first reducedto give the compound of the formula (3). The reduction can be carriedout with hydrogen in the presence of a catalyst, such as palladium,platinum or nickel, at temperatures of 40 to 90° C., or by non-noblemetals, such as tin or zinc, in the presence of an acid, preferably amineral acid, such as, for example, hydrochloric acid or sulfuric acid,at temperatures of 10 to 50° C. Preferably, the reduction is carried outwith sodium dithionite in water, in particular at pH values of 6 to 9,preferably 6.5 to 7.5, and temperatures of 15 to 45° C., preferably 20to 30° C.

The reducing agent is expediently employed in a 2- to 6-fold molaramount, based on the compounds of the formula (2).

The compounds of the formula (3) are novel and the invention likewiserelates to them.

The compounds of the formula (3) are stable in air in an acidic mediumand can be isolated as solids by filtration with suction. In a neutralmedium, the process is expediently carried out under an inert gas, forexample a nitrogen atmosphere.

The compounds of the formula (3) thus obtained are reacted with acorresponding amidation component under an inert gas atmosphere inwater, in a solvent, such as dimethylformamide, dimethylacetamide orN-methyl-pyrrolidone, or in a water/solvent mixture, or in watercontaining auxiliaries, such as, for example, ε-caprolactam, urea,surfactants, solvents of the abovementioned type and otherwater-miscible solvents, such as acetone or methyl ethyl ketone, to givecompounds of the formula (4), the radicals Z₁ and/or Z₂ defined abovebeing introduced.

The said amidation components are compounds from the series consistingof organic or inorganic acid halides, such as carboxylic acid orsulfonic acid chlorides, anhydrides, such as carboxylic acid or sulfonicacid anhydrides, isocyanates, carbonic acid esters, such aschlorocarbonic acid esters or carbonic acid diesters, ureas, carbamicacid chlorides, carboxylic acid esters, sulfonic acid esters andelectron-depleted N-containing heterocyclic compounds which containleaving groups, such as, in particular, halotriazines orhalopyrimidines.

In the case where the amidation component is a carboxylic acid chloride,the reaction is advantageously carried out at pH values of 3 to 9,preferably 4 to 8, and temperatures of 0 to 80° C., preferably 20 to 50°C. Carboxylic acid chlorides are, for example, benzoyl chloride, 3- or4-nitrobenzoyl chloride, chloroacetyl chloride, acetyl chloride,propionyl chloride or 3-(β-chloroethylsulfonyl)-benzoyl chloride.

In the case where the amidation component is an acid anhydride, thereaction is advantageously carried out at pH values of 3 to 9,preferably 4 to 8, and temperatures of 30 to 100° C., preferably 40 to60° C.

Carboxylic acid anhydrides are, for example, acetic anhydride or cycliccarboxylic acid anhydrides, such as, in particular, succinic anhydride,maleic anhydride or phthalic anhydride.

In the case where the amidation component is urea or a urea derivative,the reaction is advantageously carried out in the urea (derivative) meltor in a high-boiling solvent, such as N-methylpyrrolidone ordimethylacetamide, at temperatures of 120 to 180° C.

In the case where the amidation component is a carbamic acid chloride,such as Cl--CO--NHC₂ H₅, the reaction is advantageously carried out inwater at pH values of 4 to 7 and temperatures of 40 to 95° C.

In the case where the amidation component is a carboxylic acid ester,such as ethyl acetate, the reaction is advantageously carried out inwater or a water/solvent mixture at temperatures of 90 to 150° C. and inthe presence of acid or Lewis acid catalysts.

In the case where the amidation component is a sulfonic acid ester, suchas para-methylphenyl-SO₂ --OC₂ H₅, the reaction is advantageouslycarried out in water at pH values of 2 to 5 and temperatures of 80 to150° C.

In the case where the amidation component is a 2,4-difluoro-triazinecompound, the reaction is advantageously carried out at pH values of 3to 9, preferably 4 to 8, and temperatures of 0 to 60° C., preferably 0to 40° C.

In the case where the amidation component is a 2,4-dichloro-triazinecompound, the reaction is advantageously carried out at pH values of 3to 10, preferably 4 to 8, and temperatures of 20 to 100° C., preferably30 to 80° C.

In the case where the amidation component is a monochloro-triazinecompound, the reaction is advantageously carried out at pH values of 3to 9, preferably 4 to 8, and temperatures of 50 to 100° C., preferably60 to 90° C.

In the case where the amidation component is a monofluoro-triazinecompound, the reaction is advantageously carried out at pH values of 3to 9, preferably 4 to 8, and temperatures of 40 to 90° C., preferably 50to 70° C.

In the case where the amidation component is a di- ortrifluoro-pyrimidine compound, the reaction is advantageously carriedout at pH values of 3 to 9, preferably 4 to 8, and temperatures of 0 to60° C., preferably 20 to 40° C.

In the case where the amidation component is a carbonic acid derivative,for example an isocyanate, a chlorocarbonic acid ester or a carbonicacid ester, the reaction is advantageously carried out at pH values of 4to 8, preferably 5 to 7, and temperatures of 20 to 60° C., preferably 25to 40° C.

In the case where the amidation component is a sulfonyl chloride, thereaction is advantageously carried out at pH values of 4 to 8,preferably 5 to 7, and temperatures of 20 to 60° C., preferably 25 to40° C. Sulfonyl chlorides are, for example, 4-methylphenyl-sulfonylchloride, phenylsulfonyl chloride or 4-(acetylamino)phenylsulfonylchloride.

If several possibilities for the preparation of the same products aredescribed, the reaction with acid chlorides is the preferred procedure.

The molar ratios of amounts for the preparation of compounds of theformula (4) amidated symmetrically on both sides are: compound of theformula (3) where T=H to amidation component 1:2 to 1:6, preferably 1:2to 1:3.

Mixed condensation reactions (3)→(4) for the preparation of asymmetricdioxazines, i.e. Z₁ differs from Z₂, can be carried out by reacting thecompound of the formula (2) where T=H with an approximately 1:1 mixtureof the amidation components corresponding to the radicals Z₁ and Z₂ Theasymmetric product is obtained here as a mixture with the two symmetriccondensation products. A better and therefore preferred procedure,however, is the reaction of that compound of the formula (3) in whichT=Z₁ with the amidation component corresponding to the radical Z₂.Considerably purer uniform products are obtained in this reaction thanin the mixed condensation reaction, which is a particular advantage ofthe process variant according to the invention. For the reaction of acompound of the formula (3) where T=Z₁ with the amidation component Z₂,the said amidation component is employed in a molar ratio of 1:1 to 1:3,preferably 1:1 to 1:2, to the compound of the formula (3).

The compounds of the formula (4) are novel and the invention likewiserelates to them.

The compounds of the formula (4) are converted into the compounds of theformula (1) by oxidation. This oxidation can be carried out byatmospheric oxygen at pH values of 6 to 10, or by addition of anoxidizing agent, such as hydrogen peroxide or an alkali metalperoxodisulfate, at pH values of 4 to 7 and 20 to 60° C., preferably 25to 40° C. The amount of oxidizing agent added is expediently 2 to 6molar equivalents, based on the compound of the formula (4).

It is surprising that, in spite of an additional reduction and oxidationstep, the process according to the invention gives considerably higheryields and better product qualities than according to the prior art.

Particularly preferred triphendioxazine compounds of the formula (1) arethose of the formula (1a) ##STR12## in which M is Na, K or Li.

Particularly preferred triphendioxazine compounds of the formula (1) arethose which correspond to the formula (7a) ##STR13## in which R₁, R₂,X₁, X₂ and M have one of the abovementioned meanings;

A¹⁰ is the radical of a C₁ -C₄ -aliphatic amine, which can besubstituted by sulfo, hydroxyl or carboxyl, or the radical of a C₆ - orC₁₀ -aromatic amine, which can be substituted by SO₂ Y, 1 or 2 methoxygroups and/or 1 or 2 sulfo groups, or cyanoamino;

A²⁰ is halogen or has one of the meaning of A¹⁰ ;

A³⁰ has one of the meanings of A¹⁰ ; and

A⁴⁰ has one of the meanings of A¹⁰ or is halogen.

Such dyestuffs are known in some cases from U.S. Pat. No. 5,272,267,U.S. Pat. No. 5,438,137, U.S. Pat. No. 5,456,726 and U.S. Pat. No.5,486,607 and are suitable, for example, as reactive dyestuffs fordyeing cellulose fibers. The procedure described in the presentinvention is advantageous in respect of the yield and purity of thesedyestuffs.

Dyestuffs of the formula (7a) in which both the radicals A¹⁰ and A³⁰ are--NH--arylene--SO₂ Y, and both the radicals A²⁰ and A⁴⁰ are fluorine,chlorine, --NH--(CH₂)₂ --SO₃ H or --NH-phenylene-(SO₃ H)₁₋₂ or are aradical --NH-arylene--SO₂ Y are already known from U.S. Pat. No.5,272,267, U.S. Pat. No. 5,438,137 and Japanese Patent Application No.02238063, and are suitable, for example, as reactive dyestuffs fordyeing cellulose fibers. The procedure described in the presentinvention is particularly advantageous in respect of the yield andpurity of these dyestuffs.

Dyestuffs of the formula (7a) in which both the radicals A¹⁰ and A³⁰ arethe radical of a sulfonated phenylamine, such as --NH-phenylene-(SO₃H)₁₋₂, and both the radicals A²⁰ and A⁴⁰ are fluorine or chlorine arealready known from U.S. Pat. No. 3,883,523 and are suitable, forexample, as reactive dyestuffs for dyeing cellulose fibers. Theprocedure described in the present invention is particularlyadvantageous in respect of the yield and purity of these dyestuffs.

Those dyestuffs of the formula (7a) in which both the radicals A¹⁰ andA³⁰ are cyanoamino and the two radicals A²⁰ and A⁴⁰ are fluorine,chlorine or are a radical of the formula ##STR14## in which M, L, y andU₂ have one of the abovementioned meanings, are novel and the presentinvention therefore relates to them.

Those dyestuffs of the formula (7a) in which both the radicals A¹⁰ andA³⁰ are N(aryl)--(CH₂)₂₋₃ --SO₂ Y and both radicals A²⁰ and A⁴⁰ arefluorine or chlorine are already known from U.S. Pat. No. 5,405,947 andU.S. Pat. No. 5,484,458 and are suitable, for example, as reactivedyestuffs for dyeing cellulose fibers. The procedure described in thepresent invention is particularly advantageous in respect of the yieldand purity of these dyestuffs.

Particularly preferred dyestuffs of the formula (1) are furthermorethose dyestuffs in which the radicals Z₁ and Z₂ have different meanings,for example the compound of the formula (7b) ##STR15## in which R₁, R₂,X₁, X₂, W and M have one of the abovementioned meanings;

R₄₀ is hydrogen, C₁ -C₄ -alkyl, phenyl or sulfophenyl;

Q₁ is fluorine, chlorine, amino, C₁ -C₄ -alkoxy, phenoxy, or pyridinyl,which can be substituted by carboxyl or aminocarbonyl, or cyanoamino;

Y⁷ is β-sulfatoethyl, β-chloroethyl or vinyl;

A₃ is fluorine, chlorine, cyanoamino or amino; and

A₄ is one of the following radicals ##STR16## in which M, U₂, y and Lhave one of the abovementioned meanings.

Those dyestuffs of the formula (7b) in which the radical Q₁ iscyanoamino and at the same time W is phenylene are particularlypreferred. They are novel and the invention therefore relates to them.

Those dyestuffs of the formula (7b) in which the radical W is C₂ -C₆-alkylene and Q₁ has one of the abovementioned meanings are likewiseparticularly advantageous. They are novel and the invention thereforerelates to them.

The dyestuffs of the formula (7b) are suitable, for example, as reactivedyestuffs for dyeing cellulose fibers.

Those dyestuffs of the formula (7b) in which Q₁ is halogen and W isphenylene are already known in some cases from U.S. Pat. No. 5,272,267and U.S. Pat. No. 5,438,137. The procedure described in the invention isadvantageous in respect of the yield and purity of these dyestuffs.

Particularly preferred dyestuffs of the formula (1) are furthermore theasymmetric dyestuffs of the formula (7c) ##STR17## in which R₁, R₂, R₄₀,X₁, X₂, Q¹, Y⁷ and M have one of the abovementioned meanings;

alk is ethylene or propylene; and

Z₁ ' is C₁ -C₄ -alkylcarbonyl, C₂ -C₄ -alkenylcarbonyl, aminocarbonyl,C₁ -C₆ -alkylaminocarbonyl, C₆ -arylaminocarbonyl, C₆ -arylcarbonyl orC₆ -arylsulfonyl, which can be substituted by hydroxyl, cyano, sulfo,sulfato, carboxyl, acetylamino or SO₂ Y⁷.

Z₁ ' is, for example, acetyl, β-carboxyacryloyl, β-carboxypropionyl,3-(β-chloroethylsulfonyl)-benzoyl, phenylsulfonyl,4'-methylphenylsulfonyl, benzoyl or 2- or 4-carboxybenzoyl.

Dyestuffs of the formula (7c) are novel and the invention thereforerelates to them. They are suitable, for example, as reactive dyestuffsfor dyeing cellulose fibers.

Particularly preferred dyestuffs of the formula (1) are furthermore theasymmetric dyestuffs of the formula (7d) ##STR18## in which R₁, R₂, R₄₀,Y⁷, Z₁ ', X₁, X₂ and M have one of the abovementioned meanings.

Dyestuffs of the formula (7d) are novel and the invention thereforerelates to them. They are suitable, for example, as reactive dyestuffsfor dyeing cellulose fibers.

Particularly preferred dyestuffs of the formula (1) are furthermore theasymmetric dyestuffs of the formula (7e) ##STR19## in which R₁, R₂, X₁,X₂, Y⁷ and M have one of the abovementioned meanings;

Z₁₁ ' has one of the meanings of Z₁ '; or in which Z₁₁ ' is one of theradicals ##STR20## in which M, y, U₂, Hal and L have one of theabovementioned meanings.

Dyestuffs of the formula (7e) are novel and the invention thereforerelates to them. They are suitable, for example, as reactive dyestuffsfor dyeing cellulose fibers.

Particularly preferred dyestuffs of the formula (1) are, furthermore,the asymmetric dyestuffs of the formula (7f) ##STR21## in which B₁, B₂,B₃, R₁, R₂, X₁, X₂ and M have one of the abovementioned meanings and Z₁₁' has one of the meanings given under (7e).

Dyestuffs of the formula (7f) are novel and the invention thereforerelates to them. They are suitable, for example, as reactive dyestuffsfor dyeing cellulose fibers.

Particularly preferred dyestuffs of the formula (7f) are those in whichB₁ and B₂ are in each case fluorine.

The present invention therefore relates to triphendioxazine compounds ofthe formula (7) ##STR22## comprising the dioxazine compounds describedabove as novel and defined in claim 10.

The dyestuffs according to the invention are suitable for dyeing andprinting fiber materials. Suitable fiber materials are cellulose fibers,such as cotton, viscose or chemically modified cellulose, polyamides,such as polyamide 6 or polyamide 6,6, or protein fibers, such as wool orsilk, or blend fabrics comprising at least one of the abovementionedfiber materials, such as cotton/polyester blend fabric orcotton/polyamide blend fabric.

The dyestuffs can be applied to cellulose fibers as direct dyestuffs orreactive dyestuffs, suitable dyeing processes being exhaustion orpad-dyeing processes, such as the short-time pad-batch process or thepad-steam process, but particularly preferably exhaustion processes. Thedyestuffs can be applied to polyamide or protein fibers as aciddyestuffs or reactive dyestuffs.

Dyestuffs of the formula (1) in which at least one of the radicals Z₁and Z₂ is a reactive group from the pyrimidine series are particularlytinctorially strong and are distinguished by very good fastnesses towashing. Accompanying white laundry is stained only very little duringwashing. This finding is particularly surprising, sincetriphendioxazines to date have only moderate fastness to washing.

The suitability of the dyestuffs according to the invention for dyeingprocesses in which very small amounts of salt, for example sodiumchloride or sodium sulfate, are applied is likewise remarkable, amountsof salt to 50 to 80 g/l being customary in reactive dyeing, and evenso-called low-salt dyestuffs in any case requiring 20 to 40 g/l of salt.A loss of tinctorial strength is usually suffered with reduced amountsof salt, i.e. for ecological reasons the dyestuffs are used for dyeingunder conditions which do not correspond to their optimum. Surprisingly,it has now been found that the tinctorial strength which can be achievedfor the triphendioxazines of the formula (1) according to the inventionin which at least one of the radicals Z₁ or Z₂ is a reactive group fromthe pyrimidine series is almost independent of the amount of salt, i.e.the amount of salt employed can be reduced drastically without a loss oftinctorial strength. The invention therefore likewise relates to such aparticularly ecologically advantageous dyeing process with a greatlyreduced amount of salt of 0 to 20, preferably 5 to 15, grams ofelectrolyte salt per liter of dye solution, not taking into accountalkaline electrolyte introduced by the dyeing alkali, such as, forexample, sodium hydroxide or sodium carbonate, preferably at dyeingtemperatures of 40 to 90° C. in the exhaustion process.

EXAMPLES Example A

0.1 mol (58.5 g) of the triphendioxazine compound of the formula##STR23## is suspended in 2 l of five molar hydrochloric acid at 25° C.under a nitrogen atmosphere for some time. A total of 20 g of tin arethen added in portions in the course of 4 hours.

The mixture is subsequently stirred until the greenish-blue suspensionhas become completely brown, it being necessary to add further tin, ifappropriate, and the batch is then filtered with suction and the residueis rinsed with one normal hydrochloric acid. The moist, greenish-brownfiltercake is kept under nitrogen and is further reacted as described inthe following examples.

The compound of the formula ##STR24## or the hydrochloride thereof isobtained.

Example B

Alternatively, the compound from Example A can also be prepared byreacting the lithium salt of the triphendioxazine compound from ExampleA, prepared by dissolving the sulfonic acid with lithium hydroxide in2.5 l of water, with 38 g of sodium dithionite at pH values of 6.5 to7.5 and temperatures of 20 to 30° C. in a nitrogen inert gas atmosphere.

Example C

Alternatively, the compound of Example A can also be prepared byreacting the triphendioxazine compound at a temperature of 70° C. undera hydrogen pressure of 70 bar over a Raney nickel catalyst.

Example D

Alternatively, the compound of Example A can also be prepared byreacting the lithium salt of the triphendioxazine compound at atemperature of 70° C. under a hydrogen pressure of 70 bar over apalladium-on-charcoal catalyst.

Example E

Alternatively, the compound of Example A can also be prepared byreacting the triphendioxazine compound at a temperature of 20 to 30° C.in 2 liters of two normal hydrochloric acid and 25 g of zinc.

Example F

67 g of the lithium salt of the compound of the formula ##STR25## thepreparation of which is described in PCT/US 94/03233, are reduced with24 g of sodium dithionite in 2 l of water at a temperature of 25° C. anda pH of 6.5 to 7.5 to give the compound of the formula ##STR26## andthis compound is further reacted directly, without intermediateisolation, as described in the following examples.

Example G

75.4 g of the lithium salt of the compound of the formula ##STR27##which is known from EP-A-0 385 120/Example 319 is reduced with 38 g ofsodium dithionite in 1 l of water at a temperature of 25° C. and a pH of7 to give the compound of the formula ##STR28## and this compound isfurther reacted directly, without intermediate isolation, as describedin the following examples.

Example H

58.9 g of the lithium salt of the triphendioxazine compound9,13-dichloro-3,10-diamino-4,11-disulfo-triphendioxazine are reactedwith 15 parts of acetic anhydride in 2 l of water at a pH of 7 and atemperature of 20 to 25° C. to give the compound of the formula##STR29##

This compound is reduced with 38 g of sodium dithionite at a pH of 6 to7 and 30° C. in a nitrogen atmosphere to give a compound of the formula##STR30##

The mixture is subsequently stirred until the blue solution has becomecompletely brown, and the resulting solution is then reacted further asdescribed in the following examples.

Example I

0.1 mol (58.9 g) of the lithium salt of the triphendioxazine compound9,13-dichloro-3,10-diamino-4,11 -disulfo-triphendioxazine are reactedwith 0.25 mol (37 g) of phthalic anhydride in 2 l of water at a pH of 6to 7 and a temperature of 40 to 50° C. to give the compound of theformula ##STR31##

This compound is reduced with 37 g of sodium dithionite at a pH of 6 to7 and 35° C. in a nitrogen atmosphere to give a compound of the formula##STR32##

The mixture is subsequently stirred until the blue solution has becomecompletely brown, and the resulting solution is then reacted further asdescribed in the following examples.

The compounds mentioned in Table 1 can be prepared analogously by one ofthe procedures described above.

                  TABLE 1                                                         ______________________________________                                        1 #STR33##                                                                    2 #STR34##                                                                    Example Z.sub.1 '                                                             ______________________________________                                        J       5-Chloro-2,4-difluoro-pyrimidyl                                       K       2,4-Difluoro-pyrimidyl                                                L       Benzoyl                                                               M       3'-Nitrobenzoyl                                                       N       4'-Nitrobenzoyl                                                       O       2-Fluoro-4-(4'-sulfophenyl)amino-triazin-6-yl                         P       2-Chloro-4-(3'-sulfophenyl)amino-triazin-6-yl                         Q       β-Carboxypropionyl                                               R       β-Carboxyacryloyl                                                S       4-Chloro-2-{N-Phenyl-3'-(β-sulfatoethylsulfonyl)-propyl-                 amino}-triazin-6-yl                                                   ______________________________________                                    

Example T

0.1 mol (58.5 g) of the triphendioxazine compound of the formula##STR35## is heated at 80 to 100° C. in 1 l of 20% strength oleum forsome time, and the mixture is allowed to cool and stirred on ice at 0 to10° C. It is filtered with suction, the filtercake is suspended inwater, and sodium hydroxide solution is added until a pH of 1 to 2 isreached. The mixture is then filtered with suction again and thetriphendioxazine substance of the formula ##STR36## is isolated.

0.1 mol of the dioxazine compound prepared in the manner described issuspended in 2 l of five molar hydrochloric acid at 25° C. under anitrogen atmosphere for some time. A total of 20 g of tin are then addedin portions in the course of 4 hours. The mixture is subsequentlystirred until the greenish-blue suspension has become completely brown,the batch is then filtered with suction and the residue is rinsed withone normal hydrochloric acid. The moist, greenish-brown filtercake iskept under nitrogen and reacted further as described in the followingexamples.

The compound of the formula ##STR37## which is further reacted asdescribed in the following examples, is obtained.

Example 1

0.3 mol of 2-(2'-sulfo-phenyl)-amino-4,6-dichloro-triazine is added to0.1 mol of the leuco-dioxazine compound, prepared according to ExampleA, in 2 l of water at a temperature of about 60° C. and a pH of 4 to 5and the reaction is carried out under a nitrogen atmosphere, whilemaintaining this pH and this temperature. The nitrogen atmosphere isthen removed and stirring is continued in air until the re-oxidation iscomplete. The dyestuff of the formula ##STR38## which is isolated bysalting out with sodium chloride, is obtained. The dyestuff dyes cottonin intense brilliant violet color shades.

Example 2

0.25 mol of 2-(2',5'-disulfo-phenyl)-amino-4,6-dichloro-triazine isadded to 0.1 mol of the leuco-dioxazine compound prepared according toExample B in 2 l of water at a temperature of about 60° C. and a pH of 4to 5, and the reaction is carried out under a nitrogen atmosphere whilemaintaining the pH and temperature. The nitrogen atmosphere is thenremoved and the mixture is further stirred in air until the re-oxidationis complete. The dyestuff of the formula ##STR39## which is isolated bysalting out with sodium chloride, is obtained. The dyestuff dyes cottonin intense brilliant violet color shades.

Example 3

0.3 mol of2-(N-phenyl-2'-{β-sulfato-ethyl-sulfonyl}-ethyl)-amino-4,6-difluoro-triazine,known from EP-A-0 568 876, is added to 0.1 mol of the leuco-dioxazinecompound prepared according to Example C in 2 l of water at atemperature of 5 to 15° C. and a pH of 4 to 5, and the mixture isstirred under a nitrogen atmosphere at pH 5 and at 30 to 40° C. untilthe reaction has ended. The nitrogen atmosphere is then removed andstirring is continued in air until the re-oxidation is complete. Thedyestuff of the formula ##STR40## which is isolated by salting out withsodium chloride, is obtained. The dyestuff dyes cotton in intensebrilliant reddish-tinged blue color shades.

Example 4

0.3 mol of 4,6-dichloro-2-cyanoamino-triazine is added to 0.1 mol of theleuco-dioxazine compound prepared according to Example A in 2 L of waterat a temperature of 5 to 15° C. and a pH of 4 to 5, and the mixture isstirred under a nitrogen atmosphere at pH 5 and at 30 to 40° C. untilthe reaction has ended.

The nitrogen atmosphere is then removed and stirring is continued in airuntil the re-oxidation is complete. The dyestuff of the formula##STR41## which is isolated from the aqueous synthesis solution byevaporation, is obtained. The dyestuff is suitable as a reactivedyestuff and/or direct dyestuff and dyes cellulose fibers, such ascotton, in intense brilliant violet color shades.

Example 5

0.05 mol of the compound from Example 4 is dissolved in 1 l of water atpH 6 and at 30° C., 0.4 mol of morpholine is added and the mixture isstirred at 60 to 70° C. and at a pH of 7 to 8 for some time until thereaction has ended. The dyestuff of the formula ##STR42## which isisolated from the aqueous synthesis solution by evaporation, isobtained. The dyestuff is suitable as a direct dyestuff and dyescellulose fibers, such as cotton, in intense brilliant violet colorshades.

Examples 6-16

Further valuable reactive dyestuffs and/or direct dyestuffs (seefollowing Table 2) are obtained if the procedure is analogous to theabovementioned examples.

                  TABLE 2                                                         ______________________________________                                        3 #STR43##                                                                    Ex.                               Color shade on                              No.  A.sub.1       A.sub.2        cotton                                      ______________________________________                                         6   2-Carboxyphenyl                                                                             Chloro         violet (575 nm)                              7   3-Sulfophenyl Chloro         violet (577 nm)                              8   4-Sulfophenyl Chloro         violet (580 nm)                              9   N-Phenyl-3'-(β-                                                                        Fluoro         violet (581 nm)                                  sulfatoethyl-                                                                 sulfonyl)-propyl-amino                                                   10   Cyanoamino    Fluoro         violet (578 nm)                             11   Cyanoamino    Cyanoamino     violet (579 nm)                             12   Cyanoamino    N-Phenyl-3'-(β-sulfato-                                                                 violet (577 nm)                                                ethyl-sulfonyl)-                                                              propyl-amino                                               13   Cyanoamino    3-(β-Sulfatoethyl-                                                                      violet (580 nm)                                                sulfonyl)-phenyl-amino                                     14   Cyanoamino    N-Methyl-β-sulfoethyl-                                                                  violet (578 nm)                                                amino                                                      15   Cyanoamino    β-Sulfoethyl-                                                                           violet (578 nm)                                                amino                                                      16   Amino         β-Sulfoethyl-                                                                           violet (579 nm)                                                amino                                                      17   2-Sulfophenyl Fluoro         violet (570 nm)                             18   2-Carboxyphenyl                                                                             Fluoro         violet (572 nm)                             19   3-Sulfophenyl Fluoro         violet (567 nm)                             20   3-Carboxyphenyl                                                                             Fluoro         violet (570 nm)                             21   2,4-Disulfophenyl                                                                           Fluoro         violet (571 nm)                             22   Morpholino    Morpholino     violet (572 nm)                             23   Morpholino    β-Sulfoethylamino                                                                       violet (567 nm)                             24   β-Sulfoethylamino                                                                      β-Sulfoethylamino                                                                       violet (570 nm)                             25   β-Sulfoethylamino                                                                      3-Sulfophenyl  violet (571 nm)                             26   Morpholino    4-Sulfophenyl  violet (571 nm)                             27   3-(β-Sulfatoethyl-                                                                     Chloro         violet (578 nm)                                  sulfonyl)-phenylamino                                                    28   3-(β-Sulfatoethyl-                                                                     Fluoro         violet (579 nm)                                  sulfonyl)-phenylamino                                                    29   3-(β-Sulfatoethyl-                                                                     β-Sulfoethylamino                                                                       violet (579 nm)                                  sulfonyl)-phenylamino                                                    ______________________________________                                    

Example 17

0.4 mol of acetic anhydride is added to 0.1 mol of the leuco-dioxazinecompound prepared according to Example A in 2 l of water at atemperature of about 40° C. and a pH of 7 under a nitrogen atmosphereand the mixture is stirred for some hours until the reaction iscomplete. The nitrogen atmosphere is then removed and stirring iscontinued in air until the re-oxidation is complete. The dyestuff of theformula ##STR44## which is isolated by salting out with sodium chloride,is obtained. The dyestuff is suitable as a direct dyestuff for dyeingcotton or regenerated cellulose fibers. The dyestuff is furthermoresuitable as an acid dyestuff for dyeing wool, silk or polyamide fibers,such as, in particular, polyamide 6 and polyamide 6,6. It dyes the fibermaterials mentioned in intense brilliant magenta-colored color shades.

Example 18

0.4 mol of succinic anhydride is added to 0.1 mol of the leuco-dioxazinecompound prepared according to Example A in 2 l of water at atemperature of 40 to 50° C. and a pH of 7 under a nitrogen atmosphere,and the mixture is stirred for some hours until the reaction iscomplete. The nitrogen atmosphere is then removed and stirring iscontinued in air until the re-oxidation is complete. The dyestuff of theformula ##STR45## which is isolated by salting out with sodium chloride,is obtained. The dyestuff is suitable as a direct dyestuff for dyeingcotton or regenerated cellulose fibers. The dyestuff is furthermoresuitable as an acid dyestuff for dyeing wool, silk or polyamide fibers,such as, in particular, polyamide 6 and polyamide 6,6. It dyes the fibermaterials mentioned in intense brilliant magenta-colored color shades.The dyestuff is furthermore suitable as a synthesis intermediate productfor further dyestuffs.

Example 19

0.3 mol of 3-nitrobenzoyl chloride is added to 0.1 mol of theleucodioxazine compound prepared according to Example A in 4 l of waterat a temperature of about 60° C. and a pH of 6 to 7 and the mixture isstirred under a nitrogen atmosphere for some time, until the reactionhas ended. The nitrogen atmosphere is then removed and stirring iscontinued in air until the re-oxidation is complete. The dyestuff of theformula ##STR46## which is isolated by salting out with sodium chloride,is obtained. The dyestuff is suitable as a direct dyestuff for dyeingcotton or regenerated cellulose fibers. The dyestuff is furthermoresuitable as an acid dyestuff for dyeing wool, silk or polyamide fibers,such as, in particular, polyamide 6 and polyamide 6,6. It dyes the fibermaterials mentioned in intense brilliant magenta-colored color shades.The dyestuff is furthermore suitable as a synthesis intermediate productfor further dyestuffs.

Further valuable direct dyestuffs and/or acid dyestuffs (see followingTable 3) are obtained if the procedure is analogous to theabovementioned example.

                  TABLE 3                                                         ______________________________________                                        4 #STR47##                                                                    Example                           Color                                       No.    Z.sub.1 '    Z.sub.2 '     shade on cotton                             ______________________________________                                        20     Chloroacetyl Chloroacetyl  magenta                                     21     Propionyl    Propionyl     magenta                                     22     4-Nitrobenzoyl                                                                             4-Nitrobenzoyl                                                                              magenta                                     23     Benzoyl      Benzoyl       magenta                                     24     2-Carboxybenzoyl                                                                           2-Carboxybenzoyl                                                                            magenta                                     25     4-Carboxybenzoyl                                                                           4-Carboxybenzoyl                                                                            magenta                                     26     2-Carboxy-acryloyl                                                                         2-Carboxy-acryloyl                                                                          magenta                                     ______________________________________                                    

Example 27

0.22 mol of 4-acetylaminophenylsulfonyl chloride is added to 0.1 mol ofthe leuco compound from Example A in 2 l of water in an inert gasatmosphere at about 60° C. and at pH 6 in the course of 1 hour and themixture is stirred further until the reaction is complete. 0.2 mol ofhydrogen peroxide is then added as a 35% strength aqueous solution andthe mixture is subsequently stirred in air for some time to give thecompound of the formula ##STR48## which is suitable as a direct dyestufffor dyeing cotton.

Example 28

0.1 mol of the dried leuco compound isolated from Example A is stirredwith 7.5 mol of urea in 2 l of water in an inert gas atmosphere in themelt at about 140° C. until the reaction is complete. The reaction meltis then poured into water at 20 to 30° C., 0.2 mol of hydrogen peroxideis added as a 35% strength aqueous solution and the mixture issubsequently stirred in air for some time, until the re-oxidation iscomplete, to give the compound of the formula ##STR49## which issuitable as a direct dyestuff for dyeing cotton.

Example 29

0.4 mol of acetic anhydride is added to 0.1 mol of the leucodioxazinecompound prepared according to Example T in 2 l of water in a nitrogenatmosphere at a temperature of 30 to 35° C. and a pH of 7 and themixture is stirred for some hours, until the reaction is complete. Thenitrogen atmosphere is then removed and stirring is continued in airuntil the reoxidation is complete. The dyestuff of the formula ##STR50##which is isolated by salting out with sodium chloride, is obtained. Thedyestuff is suitable as a direct dyestuff for dyeing cotton orregenerated cellulose fibers. The dyestuff is furthermore suitable as anacid dyestuff for dyeing wool, silk or polyamide fibers, such as, inparticular, polyamide 6 and polyamide 6,6. It dyes the fiber materialsmentioned in intense brilliant magenta-colored color shades.

Example 30

0.12 mol of the compound2,4-dichloro-6-(4'-{β-sulfatoethyl-sulfonyl}-phenyl)amino-triazine isadded to 0.1 mol of the freshly prepared leuco compound from Example Funder a nitrogen atmosphere in 2 l of water at a pH of 4 to 5 and at atemperature of 40 to 50° C. The mixture is subsequently stirred under anitrogen atmosphere until the reaction is complete. Stirring is thencontinued in air at 20 to 25° C. for some time, until the re-oxidationis complete. The compound of the formula ##STR51## is obtained. Thedyestuff is isolated from the aqueous synthesis solution by salting outwith sodium chloride.

The dyestuff dyes cotton in brilliant violet color shades with goodfastnesses. The dyestuff is outstandingly suitable for exhaustiondyeings, in which the salt content in the dye liquor corresponds to 10to 30 g/l.

Example 31

0.12 mol of the compound2,4-dichloro-6-(3'-β-sulfato-ethylsulfonyl-phenyl)amino-triazine isadded to 0.1 mol of the freshly prepared leuco compound from Example Gunder a nitrogen atmosphere in 2 l of water at a pH of 5 to 6 and at atemperature of about 60° C. The mixture is subsequently stirred under anitrogen atmosphere until the reaction is complete. Stirring is thencontinued in air at 20 to 25° C. for some time, until the re-oxidationis complete. The compound of the formula ##STR52## which is isolatedfrom the aqueous synthesis solution by salting out with sodium chloride,is obtained.

The dyestuff dyes cotton in brilliant violet color shades with goodfastnesses. The dyestuff is outstandingly suitable for exhaustiondyeings, in which the salt content in the liquor corresponds to 10 to 30g/l.

Example 32

0.13 mol of the compound2,4-dichloro-6-(N-phenyl-2'-β-sulfato-ethylsulfonyl-ethyl)-amino-triazineis added to 0.1 mol of the compound from Example G in 2 l of water at apH of 5 to 6 and at a temperature of 50 to 60° C. The mixture issubsequently stirred under a nitrogen atmosphere until the reaction iscomplete. Stirring is then continued in air at 20 to 25° C. for sometime, until the re-oxidation is complete. The compound of the formula##STR53## is obtained. The dyestuff is isolated from the aqueoussynthesis solution by salting out with sodium chloride.

The dyestuff dyes cotton in brilliant violet color shades with goodfastnesses. The dyestuff is outstandingly suitable for exhaustiondyeings, in which the salt content in the dye liquor corresponds to 10to 30 g/l.

Example 33

0.15 mol of the compound2,4-difluoro-6-(N-phenyl-2'-β-sulfato-ethyl-sulfonyl-ethyl)amino-triazineis added to 0.1 mol of the compound from Example G in 2 l of water at apH of 5 to 6 and at a temperature of 0 to 10° C. The mixture issubsequently stirred under a nitrogen atmosphere, while heating at 25°C., until the reaction is complete. Stirring is then continued in air at20 to 25° C. for some time, while maintaining the pH, until there-oxidation is complete. The compound of the formula ##STR54## isobtained. The dyestuff is isolated from the aqueous synthesis solutionby salting out with sodium chloride.

The dyestuff dyes cotton in brilliant violet color shades with goodfastnesses. The dyestuff is outstandingly suitable for exhaustiondyeings, in which the salt content in the dye liquor corresponds to 10to 30 g/l.

Example 34

0.14 mol of the compound2-chloro-4-cyanoamino-6-(4'-β-sulfato-ethylsulfonyl-phenyl)amino-triazineis added to 0.1 mol of the compound from Example G in 3 l of water at apH of 5 to 5.5 and at a temperature of 60 to 70° C. The mixture issubsequently stirred under a nitrogen atmosphere at a temperature of 70to 80° C. and a pH of 4 to 5 until the reaction is complete. Stirring isthen continued in air at 20 to 25° C. for some time, until there-oxidation is complete. The compound of the formula ##STR55## isobtained. The dyestuff is isolated from the aqueous synthesis solutionby salting out with sodium chloride.

The dyestuff dyes cotton in brilliant violet color shades with goodfastnesses. The dyestuff is outstandingly suitable for exhaustiondyeings, in which the salt content in the dye liquor corresponds to 10to 30 g/l.

Example 35

0.14 mol of the compound2,4-dichloro-6-(2',5'-disulfo-phenyl)aminotriazine is added to 0.1 molof the triphendioxazine dyestuff of the formula ##STR56## in 3 l ofwater at a pH of 5 to 5.5 and at a temperature of 60 to 70° C. Themixture is subsequently stirred under a nitrogen atmosphere at atemperature of 70 to 80° C. and a pH of 4 to 5 until the reaction iscomplete. Stirring is then continued in air at 20 to 25° C. for sometime, until the reoxidation is complete. The compound of the formula##STR57## is obtained. The dyestuff is isolated from the aqueoussynthesis solution by salting out with sodium chloride.

The dyestuff dyes cotton in brilliant violet color shades with goodfastnesses. The dyestuff is outstandingly suitable for exhaustiondyeings, in which the salt content in the dye liquor corresponds to 10to 30 g/l.

Further valuable dyestuffs (see Table 4) are obtained if the procedureis analogous to the abovementioned examples, it being possible for thesequence of the reactions with respect to the two triazine radicals tobe as desired.

                  TABLE 4                                                         ______________________________________                                        5 #STR58##                                                                                                             Color                                                                         shade                                Ex.                                      on                                   No.  A.sub.1 A.sub.2    A.sub.3                                                                             A.sub.4    cotton                               ______________________________________                                        38   Chloro  Hydroxyethyl-                                                                            Chloro                                                                              3-Sulfophenyl-                                                                           violet                                            amino            amino                                           37   Chloro  N-Methyl-β-                                                                         Chloro                                                                              4-Sulfophenyl-                                                                           violet                                            sulfoethyl-      amino                                                        amino                                                            38   Fluoro  Cyanoamino Fluoro                                                                              Morpholino violet                               39   Chloro  Amino      Fluoro                                                                              2,5-Disulfo-                                                                             violet                                                             phenyl-amino                                    40   Chloro  N-Phenyl-2'-                                                                             Chloro                                                                              2,5-Disulfo-                                                                             violet                                            (β-sulfatoethyl-                                                                          phenyl-amino                                                 sulfonyl)-                                                                    ethyl-amino                                                      41   Chloro  3-(β-sulfato-                                                                       Cyano Cyanoamino violet                                            ethyl)-sulfonyl-                                                                         amino                                                              phenyl-amino                                                     42   Fluoro  N-Phenyl-2'-                                                                             Chloro                                                                              Cyanoamino violet                                            (β-sulfatoethyl-                                                         sulfonyl)-                                                                    ethyl-amino                                                      43   Chloro  2,5-Disulfo-                                                                             Fluoro                                                                              Cyanoamino violet                                            phenyl-amino                                                     44   Chloro  2,5-Disulfo-                                                                             Fluoro                                                                              N-Phenyl-2'-                                                                             violet                                            phenyl-amino     (β-sulfatoethyl-                                                         sulfonyl)-ethyl-                                                              amino                                           45   Chloro  2,5-Disulfo-                                                                             Chloro                                                                              4-(β-sulfatoethyl)-                                                                 violet                                            phenyl-amino     sulfonyl-                                                                     phenyl-amino                                    ______________________________________                                    

Example 46

0.12 mol of the compoundN-phenyl-2,4-dichloro-6-{2'-β-sulfato-ethylsulfonyl-ethyl}-amino-triazineis added to 0.1 mol of the freshly prepared leuco compound from ExampleH in 2 l of water at a pH of 4 to 5 and at a temperature of 20 to 27° C.The mixture is subsequently stirred under a nitrogen atmosphere untilthe reaction is complete. Stirring is then continued in air at 20 to 25°C. for some time, until the re-oxidation is complete. The compound ofthe formula ##STR59## is obtained. The dyestuff is isolated from theaqueous synthesis solution by salting out with sodium chloride.

The dyestuff dyes cotton in brilliant violet color shades with goodfastnesses. The dyestuff is outstandingly suitable for exhaustiondyeings, in which the salt content in the dye liquor corresponds to 10to 30 g/l.

Example 47

The dyestuff from Example 46 is likewise obtained if 0.15 mol ofcyanuric chloride, metered in as a solution in acetone, is added to 0.1mol of the compound from Example H in 3 l of water at a pH of 6 to 7 andat a temperature of 20 to 30° C., and the mixture is subsequentlystirred at 40° C. and pH 7 for some time, until the reaction has ended.0.15 mol of N-phenyl-(2-β-sulfato-ethylsulfonyl)-ethyl-amine is thenadded at pH 5 and the mixture is subsequently stirred under a nitrogenatmosphere at pH 5 and about 50° C. for some time, until the reactionhas eroded. The dyestuff is then re-oxidized as described above andisolated as in Example 46.

Example 48

0.15 mol of succinic anhydride is added to 0.1 mol of thetriphendioxazine dyestuff of the formula ##STR60## which is known fromEP-A1-0 628 606, Example 1, in 2 l of water at a pH of 6 to 7 and at atemperature of 30 to 40° C. The reaction is carried out at 50 to 60° C.and a pH of 7 and the mixture is subsequently stirred under a nitrogenatmosphere until the reaction is complete. Stirring is then continued inair at 20 to 25° C., with the addition of 0.1 mol of potassiumperoxodisulfate, for some time, until the re-oxidation is complete. Thecompound of the formula ##STR61## is obtained. The dyestuff is isolatedfrom the aqueous synthesis solution by salting out with sodium chloride.

The dyestuff dyes cotton in brilliant violet color shades with goodfastnesses. The dyestuff is outstandingly suitable for exhaustiondyeings, in which the salt content in the dye liquor corresponds to 10to 30 g/l.

Example 49

0.14 mol of the compound2,4-difluoro-6{-N-phenyl-2'-β-sulfato-ethylsulfonyl-ethyl}-amino-triazineis added to 0.1 mol of the freshly prepared compound from Example H in 2l of water at a pH of 5 to 6 and at a temperature of 20 to 25° C. Themixture is subsequently stirred under a nitrogen atmosphere until thereaction is complete. Stirring is then continued in air at 20 to 25° C.for some time, until the re-oxidation is complete.

The compound of the formula ##STR62## is obtained. The dyestuff isisolated from the aqueous synthesis solution by salting out with sodiumchloride.

The dyestuff dyes cotton in brilliant violet color shades with goodfastnesses. The dyestuff is outstandingly suitable for exhaustiondyeings, in which the salt content in the dye liquor coresponds to 10 to20 g/l.

Example 50

0.13 mol of the compound 3-(β-chloroethylsulfonyl)-benzoyl chloride isadded to 0.1 mol of the compound from Example F in 2.5 l of water at apH of 6 and a temperature of 25° C. The mixture is then heated to 40° C.and subsequently stirred at this temperature under a nitrogenatmosphere, while maintaining a pH of 6, until the reaction is complete.Stirring is then continued in air at 20 to 25° C. for some time, untilthe re-oxidation is complete. The compound of the formula ##STR63## isobtained. The dyestuff is isolated from the aqueous synthesis solutionby salting out with sodium chloride.

The dyestuff dyes cotton in brilliant violet color shades with goodfastnesses. The dyestuff is outstandingly suitable for exhaustiondyeings, in which the salt content in the dye liquor corresponds to 10to 30 g/l.

Further examples are shown in Table 5 which are carried out analogously.

                  TABLE 5                                                         ______________________________________                                        6 #STR64##                                                                                                           Color                                                                         shade                                  Ex.                                    on                                     No.  R         A.sub.1   A.sub.2       cotton                                 ______________________________________                                        51   β-Carboxy-                                                                         Chloro    N-Phenyl-2-   violet                                      ethyl               (β-sulfatoethylsulfonyl)-                                                ethyl-amino                                          52   β-Carboxy-                                                                         Chloro    N-Phenyl-2-   violet                                      vinyl               (β-sulfatoethylsulfonyl)-                                                ethyl-amino                                          53   2-Carboxy-                                                                              Chloro    N-Phenyl-2-   violet                                      phenyl              (β-sulfatoethylsulfonyl)-                                                ethyl-amino                                          54   Phenyl    Cyanamino N-Phenyl-2-   violet                                                          (β-sulfatoethylsulfonyl)-                                                ethyl-amino                                          55   2-Carboxy-                                                                              Chloro    N-Phenyl-2-   violet                                      phenyl              (β-sulfatoethylsulfonyl)-                                                ethyl-amino                                          56   Methyl    Chloro    N-Phenyl-3-   violet                                                          (β-sulfoethylsulfonyl)-                                                  propyl-amino                                         57   Methyl    Chloro    N-(3-Sulfo-phenyl)-3-                                                                       violet                                                          (β-sulfato-ethyl-sulfonyl)-                                              propyl-amino                                         58   Ethyl     Chloro    N-Phenyl-3-   violet                                                          (β-sulfatoethylsulfonyl)-                                                propyl-amino                                         59   Ethyl     Fluoro    N-Phenyl-3-   violet                                                          (β-sulfatoethylsulfonyl)-                                                propyl-amino                                         60   Ethyl     Fluoro    N-Methyl-β-sulfoethyl-                                                                 violet                                                          amino                                                61   Methyl    Fluoro    N-Methyl-2-(β-sulfatoethyl-                                                            violet                                                          sulfonyl)-ethylamino                                 62   Ethyl     Fluoro    N-Methyl-2-(β-sulfatoethyl-                                                            violet                                                          sulfonyl)-ethylamino                                 63   β-Carboxy-                                                                         Fluoro    N-Methyl-2-(β-sulfatoethyl-                                                            violet                                      ethyl               sulfonyl)-ethylamino                                 64   β-Carboxy-                                                                         Fluoro    N-Methyl-2-(β-sulfatoethyl-                                                            violet                                      vinyl               sulfonyl)-ethylamino                                 65   3-(β-Chloro                                                                        Chloro    β-Sulfoethyl-amino                                                                     violet                                      ethyl-                                                                        sulfonyl)-                                                                    phenyl                                                                   66   3-(β-Chloro                                                                        Fluoro    β-Sulfoethyl-amino                                                                     violet                                      ethyl-                                                                        sulfonyl)-                                                                    phenyl                                                                   67   3-(β-Chloro                                                                        Chloro    N-Methyl-β-sulfoethyl-                                                                 violet                                      ethyl-              amino                                                     sulfonyl)-                                                                    phenyl                                                                   68   3-(β-Chloro                                                                        Chloro    2,5-Disulfo-phenyl-amino                                                                    violet                                      ethyl-                                                                        sulfonyl)-                                                                    phenyl                                                                   69   3-(β-Chloro-                                                                       Chloro    4-Sulfo-phenyl-amino                                                                        violet                                      ethyl-                                                                        sulfonyl)-                                                                    phenyl                                                                   70   3-(β-Chloro-                                                                       Cyanoamino                                                                              Morpholino    violet                                      ethyl-                                                                        sulfonyl)-                                                                    phenyl                                                                   71   3-(β-Chloro                                                                        Cyanoamino                                                                              Cyanoamino    violet                                      ethyl-                                                                        sulfonyl)-                                                                    phenyl                                                                   72   3-(β-Chloro                                                                        Chloro    4-(β-Sulfatoethyl)sulfonyl-                                                            violet                                      ethyl-              phenyl-amino                                              sulfonyl)-                                                                    phenyl                                                                   73   3-(β-Chloro                                                                        Chloro    Amino         violet                                      ethyl-                                                                        sulfonyl)-                                                                    phenyl                                                                   74   3-(β-Chloro                                                                        β-Sulfoethyl-                                                                      β-Sulfoethylamino                                                                      violet                                      ethyl-    amino                                                               sulfonyl)-                                                                    phenyl                                                                   75   3-(β-Chloro                                                                        N-Methyl- N-Methyl-β-sulfoethyl-                                                                 violet                                      ethyl-    β-sulfoethyl-                                                                      amino                                                     sulfonyl)-                                                                              amino                                                               phenyl                                                                   ______________________________________                                    

Example 76

0.12 mol of the compound 3-(β-chloroethylsulfonyl)-benzoyl chloride isadded to 0.1 mol of the freshly prepared leuco compound from Example Hin 4 l of water at a pH of 5 and a temperature of 25° C. The mixture isheated to 40° C. and subsequently stirred at this temperature under anitrogen atmosphere, while maintaining the pH, until the reaction iscomplete. Stirring is then continued in air at 20 to 25° C., with theaddition of 0.1 mol of potassium peroxodisulfate, for some time, untilthe re-oxidation is complete. The compound of the formula ##STR65## isobtained. The dyestuff dyes cotton in brilliant magenta-colored colorshades with good fastnesses. The dyestuff is outstandingly suitable forexhaustion dyeings, in which the salt content in the dye liquorcorresponds to 10 to 20 g/l.

Example 77

0.12 mol of succinic anhydride is added to 0.1 mol of the leuco compoundfrom Example M in 2 l of water at a pH of 7 and at a temperature of 20to 25° C. under a nitrogen atmosphere, and the mixture is subsequentlystirred at 35 to 40° C. for some time, while maintaining the pH, untilthe condensation has ended. The nitro group is then reduced in thecustomary manner with H₂ (1 bar) over a Pd-on-charcoal catalyst. Themixture is then subsequently stirred in air for some time, until there-oxidation to the triphendioxazine compound is complete. The compoundof the formula ##STR66## which is isolated by salting out with sodiumchloride, is obtained. The resulting product is then dissolved at pH 5to 6 and at a temperature of 15 to 20° C., and 0.1 mol of5-chloro-2,4,6-difluoro-pyrimidine is subsequently added. Stirring isthen continued in air at 20 to 25° C. for some time, until the reactionis complete. The compound of the formula ##STR67## is obtained. Thedyestuff dyes cotton in brilliant magenta-colored color shades with goodfastnesses. The dyestuff is outstandingly suitable for exhaustiondyeings, in which the salt content in the dye liquor corresponds to 10to 20 g/l.

The following Table 6 contains further examples according to the formula##STR68## which are prepared in an analogous manner.

                  TABLE 6                                                         ______________________________________                                                                             Color                                                                         shade                                    Ex.                                  on                                       No.  R.sub.1     R.sub.2             cotton                                   ______________________________________                                        78   Ethyl       3(β-Chloroethylsulfonyl)-phenyl                                                              magenta                                  79   Phenyl      "                   magenta                                  80   4-Carboxyphenyl                                                                           "                   magenta                                  81   2-Carboxyphenyl                                                                           "                   magenta                                  82   2-Carboxyethyl                                                                            "                   magenta                                  83   2-Carboxyvinyl                                                                            "                   magenta                                  84   3-(β-Chloroethyl-                                                                    "                   magenta                                       sulfonyl)-phenyl                                                         85   Methyl      3-(2',4'-Difluoropyrimidin-6'-yl)-                                                                magenta                                                   amino-phenyl                                                 86   Ethyl       3-(2',4'-Difluoropyrimidin-6'-yl)-                                                                magenta                                                   amino-phenyl                                                 87   Phenyl      3-(5'-Chloro-2',4'-difluoro-                                                                      magenta                                                   pyrimidin-6'-yl)-amino-phenyl                                88   4-Carboxyphenyl                                                                           3-(5'-Cyano-2',4'-dichloro-                                                                       magenta                                                   pyrimidin-6'-yl)-amino-phenyl                                89   2-Carboxyphenyl                                                                           3-(2',4',5'-Trichloro-pyrimidin-6'-                                                               magenta                                                   yl)-amino-phenyl                                             90   2-Carboxyethyl                                                                            4-(2',4'-Difluoropyrimidin-6'-                                                                    magenta                                                   yl)-amino-phenyl                                             91   2-Carboxyvinyl                                                                            4-(2',4'-Difluoropyrimidin-6'-                                                                    magenta                                                   yl)-amino-phenyl                                             92   Methyl      3-(2'-β-Sulfoethyl-4'-fluoro-triazin-                                                        magenta                                                   6'-yl)-amino-phenyl                                          93   Ethyl       3-(2'-amino-4'-chloro-triazin-6'-                                                                 magenta                                                   yl)-amino-phenyl                                             94   β-Carboxyethyl                                                                       3(2'-{2",5"-disulfophenyl}-                                                                       magenta                                                   amino-4'-chloro-triazin-6'-yl)-amino-                                         phenyl                                                       95   2-Carboxy-phenyl                                                                          3-(2'-{4"-sulfonphenyl}amino-4'-                                                                  magenta                                                   chloro-triazin-6'-yl)-amino-phenyl                           96   Methyl      3-(2'-N-Phenyl-{2"-(β-sulfatoethyl)-                                                         magenta                                                   sulfonyl-ethyl}amino-4'-chloro-                                               triazin-6'-yl)-amino-phenyl                                  97   Methyl      3-(2'-N-Phenyl-{3"-(β-sulfatoethyl)-                                                         magenta                                                   sulfonyl-propyl}amino-4'-chloro-                                              triazin-6'-yl)-amino-phenyl                                  ______________________________________                                    

Example 98

0.14 mol of 5-chloro-2,4,6-trifluoro-pyrimidine is added to 0.1 mol ofthe compound from Example Q in 2 l of water at a pH of 5 to 6 and atemperature of 10 to 20° C. The mixture is then heated to 40° C. andsubsequently stirred under a nitrogen atmosphere until the reaction iscomplete. Stirring is then continued in air at 20 to 25° C. for sometime, until the re-oxidation is complete. The compound of the formula##STR69## is obtained. The dyestuff is isolated from the aqueoussynthesis solution by salting out with sodium chloride.

The dyestuff dyes cotton in brilliant violet color shades with goodfastnesses. The dyestuff is outstandingly suitable for exhaustiondyeings, in which the salt content in the dye liquor corresponds to 10to 30 g/l.

Example 99

0.2 mol of 5-chloro-2,4,6-trifluoro-pyrimidine is added to 0.1 mol ofthe compound from Example F in 3 to 4 l of water at a pH of 5 to 6 andat a temperature of 18 to 22° C. The mixture is subsequently stirredunder a nitrogen atmosphere until the reaction is complete. Stirring isthen continued in air at 20 to 25° C. for some time, until there-oxidation is complete.

The compound of the formula ##STR70## is obtained. The dyestuff isisolated from the aqueous synthesis solution by salting out with sodiumchloride. The dyestuff dyes cotton in brilliant violet color shades withgood fastnesses. The dyestuff is outstandingly suitable for exhaustiondyeings, in which the salt content in the dye liquor corresponds to 10to 30 g/l.

Table 7 shows further valuable dyestuffs of the formula ##STR71## whichare prepared in an analogous manner.

                  TABLE 7                                                         ______________________________________                                                                                Color                                 Ex.                                     shade on                              No.  B.sub.1 B.sub.2 B.sub.3                                                                              Z           cotton                                ______________________________________                                        100  Fluoro  Fluoro  Hydrogen                                                                             Acetyl      magenta                               101  Chloro  Chloro  Cyano  Acetyl      magenta                               102  Chloro  Chloro  Chloro Propionyl   magenta                               103  Fluoro  Hydro-  Chloro Propionyl   magenta                                            gen                                                              104  Fluoro  Fluoro  Hydrogen                                                                             Propionyl   magenta                               105  Fluoro  Fluoro  Hydrogen                                                                             β-Carboxypropionyl                                                                   magenta                               106  Fluoro  Fluoro  Hydrogen                                                                             "           magenta                               107  Fluoro  Fluoro  Hydrogen                                                                             β-Carboxyacryloyl                                                                    magenta                               108  Fluoro  Fluoro  Hydrogen                                                                             "           magenta                               109  Fluoro  Fluoro  Chloro 2-Chloro-4-amino-                                                                         magenta                                                           triazin-6-yl                                      110  Fluoro  Fluoro  Chloro 2-Chloro-4-β-sulfo-                                                                  magenta                                                           ethyl-amino-triazin-                                                          6-yl                                              111  Fluoro  Fluoro  Hydrogen                                                                             2-Fluoro-4-{N-methyl-                                                                     magenta                                                           β-sulfo-ethylamino}-                                                     triazin-6-yl                                      112  Fluoro  Fluoro  Hydrogen                                                                             2-Chloro-4-cyano-                                                                         magenta                                                           amino-triazin-6-yl                                113  Fluoro  Hydro-  Chloro 5-Chloro-2-fluor-                                                                         magenta                                            gen            pyrimidin-6-yl                                    ______________________________________                                    

Example 114

0.65 mol of 5-chloro-2,4,6-trifluoro-pyrimidine is added to 0.2 mol ofthe lithium salt of the leuco compound from Example A in 4 l of water ata pH of 6.5 to 7 and at 25° C., lithium hydroxide solution constantlybeing metered in to maintain the pH at pH 7. The mixture is subsequentlystirred until the reaction is complete, and the dyestuff of the formula##STR72## is isolated by salting out with sodium chloride. The dyestuffdyes cotton in brilliant, very reddish-tinged blue color shades in veryhigh intensities and with good fastnesses, of which the fastnesses towashing are to be emphasized in particular. The fact that the dyestuffscan be used for dyeing with a very small amount of salt, for examplewith 5 to 10 g/l of sodium sulfate, is particularly advantageous, inparticular with respect to ecology.

Example 115

0.5 mol of 2,4,6-trifluoro-pyrimidine is added to 0.2 mol of the lithiumsalt of the leuco compound from Example A in 3.5 l of water at about 27°C. and a pH of 6.8 to 7.2, lithium hydroxide solution constantly beingmetered in to maintain the pH at pH 7. The mixture is subsequentlystirred until the reaction is complete, and the dyestuff of the formula##STR73## is isolated by salting out with sodium chloride. The dyestuffdyes cotton in brilliant, very reddish-tinged blue color shades in veryhigh intensities and with good fastnesses, of which the fastnesses towashing are to be emphasized in particular. The fact that the dyestuffcan be used for dyeing with a very small amount of salt, for examplewith 5 to 10 g/l of sodium sulfate, is particularly advantageous, inparticular with respect to ecology.

Further reactive dyestuffs are obtained (see the following Table 8), ifthe procedure is analogous to the preceding examples.

                  TABLE 8                                                         ______________________________________                                        7 #STR74##                                                                    Ex. No.                                                                              X.sub.1    X.sub.2  X.sub.3                                                                             Color shade                                  ______________________________________                                        116    Chloro     Chloro   Chloro                                                                              very reddish-tinged                                                           blue                                         117    Chloro     Chloro   Cyano very reddish-tinged                                                           blue                                         118    Fluoro     Fluoro   Cyano very reddish-tinged                                                           blue                                         119    Methylsulfonyl                                                                           Methyl   Chloro                                                                              very reddish-tinged                                                           blue                                         120    Hydrogen   Fluoro   Chloro                                                                              very reddish-tinged                                                           blue                                         ______________________________________                                    

We claim:
 1. A triphendioxazine compound of the formula ( 7) ##STR75##in which R₁ is hydrogen or C₁ -C₄ -alkyl, which is optionallysubstituted by 1 or 2 substituents selected from the group consisting ofhydroxyl, C₁ -C₄ -alkoxy, sulfato and sulfo;R₂ has one of the meaningsof R₁ ; X₁ is halogen, hydrogen, C₁ -C₆ -alkyl, phenyl, phenoxy or C₁-C₄ -alkoxy; X₂ has one of the meanings of X₁ ; M is hydrogen or analkali metal and Z₁ and Z₂ are the following combinations (7a) to (7e):##STR76## in which A¹⁰ and A³⁰ are each cyanoamino;A²⁰ and A⁴⁰ arefluorine or chlorine, or are a compound of the formulae ##STR77## inwhich L is hydroxyl, sulfo, carboxyl or sulfato; U₂ is a chemical bond,methylene, --O--, --NH--, >N(CH₂)₂ OH, --S-- or --SO₂ --and y is thenumber 1 or 2; ##STR78## in which W₁ is C₂ -C₆ -alkylene; Q₁ isfluorine, chlorine, amino, C₁ -C₄ -alkoxy, phenoxy, or pyridyl, which isoptionally substituted by carboxyl or aminocarbonyl, or cyanoamino; Y⁷is β-sulfatoethyl, β-chloroethyl or vinyl; R₄₀ is hydrogen, C₁ -C₄-alkyl, phenyl or sulfophenyl; A₄ is one of the radicals ##STR79## andA₃ is fluorine, chlorine, amino or cyanoamino; or in which Y⁷, R₄, A₄and A₃ have the abovementioned meanings and Q₁ is cyanoamino and W₁ isphenylene; ##STR80## in which R₄₀, Q¹ and Y⁷ are defined as above;alk isethylene or propylene; and Z₁ ' is C₁ -C₄ -alkylcarbonyl, C₂ -C₄-alkenylcarbonyl, aminocarbonyl, C₁ -C₆ -alkylaminocarbonyl, C₆-aryl-amirocarbonyl, C₆ -arylsulfonyl or C₆ -aryicarbonyl, which areoptionally substituted by hydroxyl, cyano, sulfo carboxyl, sulfato,acetylamino or SO₂ Y⁷ ; ##STR81## in which R₄₀, Y⁷ and Z₁ ' are definedas above; ##STR82## in which Y⁷ is defined as above and Z₁₁ ' has one ofthe meanings of Z₁ ' or Z₁₁ ' is one of the radicals ##STR83## in whichHal is fluorine or chlorine.
 2. A triphendioxazine compound of theformula (7) ##STR84## in which R₁ is hydrogen or C₁ -C₄ -alkyl, which isoptionally substituted by 1 or 2 substituents selected from the groupconsisting of hydroxyl, C₁ -C₄ -alkoxy, sulfato and sulfo;R₂ has one ofthe meanings of R₁ ; X₁ is halogen, hydrogen, C₁ -C₆ -alkyl, phenyl,phenoxy or C₁ -C₄ -alkoxy; X₂ has one of the meanings of X₁ ; M ishydrogen or an alkali metal and Z₁ and Z₂ are the combination of (7f);##STR85## in which Z₁₁ ' is Z₁ ', C₁ -C₄ -alkylcarbonyl, C₂ -C₄-alkenylcarbonyl, aminocarbonyl, C₁ -C₆ -alkylaminocarbonyl, C₆-aryl-aminocarbonyl, C₆ -arylsulfonyl or C₆ -arylcarbonyl, which areoptionally substituted by hydroxyl, cyano, sulfo, carboxyl, sulfato,acetylamino or SO₂ Y⁷ ; orZ₁₁ ' is one of the radicals ##STR86## Y⁷ isβ-sulfatoethyl, β-chloroethyl or vinyl; B₁ is hydrogen, chlorine,fluorine, trichloromethyl, trifluoromethyl or methylsulfonyl; B₂ ishydrogen, chlorine, methyl, methylsulfonyl or fluorine and B₃ ishydrogen, cyano, fluorine or chlorine, with the proviso that at leastone of the radicals B₁ or B₂ is a leaving group selected from the groupconsisting of fluorine, chlorine and methylsulfonyl.
 3. The compound asclaimed in claim 1, wherein R₁ and R₂ are hydrogen.
 4. The compound asclaimed in claim 1, wherein X₁ and X₂ are chlorine.
 5. The compound asclaimed in claim 1, wherein M is hydrogen.
 6. The compound as claimed inclaim 1, wherein the compound is of the formula ##STR87##
 7. Thecompound as claimed in claim 6, wherein M is hydrogen.
 8. A method ofdyeing or printing fiber materials of cellulose, polyamides, proteins ormixtures of said fiber materials comprising the step of contacting saidfiber materials with a triphendioxazine compound as claimed in claim 1.9. The method as claimed in claim 8, wherein the dyeing or printingtakes place in the presence of 0 to 20 grams of an electrolyte salt perliter of dye solution.
 10. A method of dyeing or printing fibermaterials of cellulose, polyamides, proteins or mixtures of said fibermaterials comprising the step of contacting said fiber materials with atriphendioxazine compound as claimed in claim
 2. 11. The method asclaimed in claim 10, wherein the dyeing or printing takes place in thepresence of 0 to 20 grams of an electrolyte salt per liter of dyesolution.